US6479710B2 - Method of catalyzing a gas phase reaction using an acid-base catalyst composed of vanadium pentoxide hydrate - Google Patents

Method of catalyzing a gas phase reaction using an acid-base catalyst composed of vanadium pentoxide hydrate Download PDF

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US6479710B2
US6479710B2 US09/267,396 US26739699A US6479710B2 US 6479710 B2 US6479710 B2 US 6479710B2 US 26739699 A US26739699 A US 26739699A US 6479710 B2 US6479710 B2 US 6479710B2
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base catalyst
solid acid
vanadium pentoxide
reactions
pentoxide hydrate
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Nobuji Kishimoto
Etsushige Matsunami
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Nippon Shokubai Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8472—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/02—Amorphous compounds
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/78—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by stacking-plane distances or stacking sequences
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C01P2006/82—Compositional purity water content

Definitions

  • the present invention relates to a solid acid-base catalyst, which is suitably provided for various reactions, such as syntheses of an olefin (alkene) or an ether through a dehydration reaction of an alcohol, syntheses of an aldehyde or a ketone through a dehydrogenation reaction of an alcohol, hydration and isomerization reactions of olefin, alkylation, esterification, amidation, acetalization, amination, hydrogen shift reactions, aldol condensation reactions and polymerization reactions.
  • various reactions such as syntheses of an olefin (alkene) or an ether through a dehydration reaction of an alcohol, syntheses of an aldehyde or a ketone through a dehydrogenation reaction of an alcohol, hydration and isomerization reactions of olefin, alkylation, esterification, amidation, acetalization, amination, hydrogen shift reactions, aldol condensation reactions and polymerization reactions.
  • a solid acid-base catalyst such as zeolite, silica-alumina and titania-silica, and a solid base catalyst, such as magnesium oxide and calcium oxide are known.
  • the above conventional solid acid catalyst also has a disadvantage that its activity is decreased due to deactivation caused by carbon deposition at the time of reaction.
  • solid acid catalyst and a solid base catalyst which are capable of being prepared easily with excellent reproducibility and of displaying catalytic activity under mild reaction conditions, without deactivation, as well as solid acid-base cooperative catalyst which has both an acid point and a base point, that is peculiar to a solid catalyst, and highly selectively produces reactions through a concerted action of both active points (hereinafter, these catalysts are referred to as solid acid-base catalysts).
  • the present invention was invented based upon the above conventional problems, and it is an object of the present invention to provide to provide a new solid acid-base catalyst, which is capable of being prepared easily with excellent reproducibility and is capable of displaying catalytic activity under mild reaction conditions and whose activity is hard to be lowered due to deactivation.
  • a solid acid-base catalyst containing vanadium pentoxide hydrate sufficiently displays catalytic activity under mild conditions for various reactions, such as the syntheses of olefins or ethers through dehydration reactions of alcohols, syntheses of aldehydes or ketones through dehydrogenation reactions of alcohols, hydration and isomerization reactions of olefins, alkylations, esterifications, amidations, acetalizations, aminations, hydrogen shift reactions, aldol condensation reactions and polymerization reactions. Then, the present invention was completed.
  • the solid acid-base catalyst of the present invention is characterized by containing vanadium pentoxide hydrate.
  • vanadium pentoxide hydrate has a composition which is represented by the following general formula (1):
  • n 0.1-3.
  • the solid acid-base catalyst can display catalytic activity under mild conditions for various reactions, such as syntheses of olefins or ethers through dehydration reactions of alcohols, syntheses of aldehydes or ketones through dehydrogenation reactions of alcohols, hydrations and isomerization reactions of olefins, alkylations, esterifications, amidations, acetalizations, aminations, hydrogen shift reactions, aldol condensation reactions, and polymerization reactions.
  • various reactions such as syntheses of olefins or ethers through dehydration reactions of alcohols, syntheses of aldehydes or ketones through dehydrogenation reactions of alcohols, hydrations and isomerization reactions of olefins, alkylations, esterifications, amidations, acetalizations, aminations, hydrogen shift reactions, aldol condensation reactions, and polymerization reactions.
  • the vanadium pentoxide hydrate has a layered structure and is obtained by intercalating at least one kind of substance, which is selected from a group composed of metallic ions, ammonium ions and metal complexes. Moreover, it is desirable that the vanadium pentoxide hydrate has a layered structure and is obtained by intercalating an organic substance between layers. Further, it is desirable that the organic substance is a compound containing nitrogen.
  • the solid acid-base catalyst can be suitably applied to various reactions, such as syntheses of olefins or ethers through dehydration reactions of alcohols, syntheses of aldehydes or ketones through dehydrogenation reactions of alcohols, hydrations and isomerization reactions of olefins, alkylations, esterifications, amidations, acetalizations, aminations, hydrogen shift reactions, aldol condensation reactions, and polymerization reactions.
  • the vanadium pentoxide hydrate is obtained such that after ion exchange of a vanadate aqueous solution is made by using a proton-type cation exchange resin, the ion-exchanged solution is polycondensed and is dried. Moreover, it is secondarily preferable that the vanadium pentoxide hydrate is arranged by adding mineral acid to a vanadate aqueous solution or by hydrolyzing vanadyl alkoxide.
  • the solid acid-base catalyst has excellent properties and the catalytic activity can be further improved, a more remarkable catalytic activity can be displayed under mild reaction conditions. Therefore, the solid acid-base catalyst can be suitably applied to various reactions, such as syntheses of olefins or ethers through dehydration reactions of alcohols, syntheses of aldehydes or ketones through dehydrogenation reactions of alcohols, hydrations and isomerization reactions of olefins, alkylations, esterifications, amidations, acetalizations, aminations, hydrogen shift reactions, aldol condensation reactions, and polymerization reactions.
  • various reactions such as syntheses of olefins or ethers through dehydration reactions of alcohols, syntheses of aldehydes or ketones through dehydrogenation reactions of alcohols, hydrations and isomerization reactions of olefins, alkylations, esterifications, amidations, acetalizations, aminations, hydrogen shift reactions,
  • FIG. 1 shows an X-ray diffraction spectrum of a solid acid-base catalyst obtained in one example of the present invention.
  • a solid acid catalyst, a solid base catalyst and a solid acid-base cooperative catalyst are generically called a solid acid-base catalyst.
  • a solid acid-base catalyst of the present invention contains vanadium pentoxide hydrate, and it is desirable that such vanadium pentoxide hydrate is contained therein in the form of a xerogel (dry gel) represented by the above-mentioned general formula (1) in respect of easy handling at the time of application to reactions.
  • “n” of the general formula (1) is not particularly limited as long as it is in the range of 0.1-3.
  • the vanadium pentoxide hydrate of the present invention is different from vanadium pentoxide anhydride, which is widely used as a chief component of catalysts for oxidations and other reactions, in crystal structure and various properties. It is known that vanadium pentoxide anhydride also has acidity but it is very slight acidity, so that a display of its solid acid-base catalytic activity is on an extremely low level compared with the vanadium pentoxide hydrate in the present invention.
  • the shape of the solid acid-base catalyst is not particularly limited, but in the case where the solid acid-base catalyst is used as a fixed bed, for example, it is desirable that after the solid acid-base catalyst is ground by a ball mill or the like, the powder is molded so as to have a fixed shape according to a shape of a reactor. Moreover, it is desirable that the above molded form is crushed, for example, so as to have a grain diameter of a suitable mesh. Furthermore, the content of the vanadium pentoxide hydrate in the solid acid-base catalyst is not particularly limited.
  • the solid acid-base catalyst of the present invention can be obtained by various methods. Examples of these methods are a method of treating a vanadate aqueous solution with a proton type cation exchange resin and polycondensing and drying it (i.e., an ion-exchange polymerization method), a method of treating a vanadate aqueous solution with a mineral acid, such as nitric acid, sulfuric acid or hydrochloric acid so as to obtain a precipitate and filtering and drying the precipitate (i.e., a mineral acid treatment), a method of drying a gel which is obtained by hydrolyzing a vanadyl alkoxide, such as vanadyl ethoxide, vanadyl isopropoxide and vanadyl butoxide (i.e., an alkoxide method), and a method of heating V 2 O 5 at a high temperature and melting it, and rapidly contacting it with water (i.e., a melt quench method).
  • the vanadium pentoxide hydrate obtained by any of these methods can be used as a solid acid-base catalyst, but in particularly, the ion-exchange polymerization method is preferable.
  • a solid acid-base catalyst obtained contains a residual group of vanadate and a mineral acid as impurities, a vanadium pentoxide hydrate having constant properties cannot be obtained. Furthermore a filtrate obtained by filtration contains a large amount of vanadium, so that the yield of the vanadium pentoxide hydrate is low.
  • vanadyl alkoxide which is a raw material is expensive, and a large amount of organic solvents, such as alcohol, is required.
  • the properties of the solid acid-base catalyst obtained under the condition of hydrolyzing gelation are greatly changed, so it is difficult to obtain a solid acid-base catalyst having constant properties.
  • the yield is extremely low when a general apparatus is used, so it is necessary to use a special and expensive apparatus.
  • a solid acid-base catalyst having constant properties can be obtained quantitatively with good reproducibility by using a simple apparatus, this method is advantageous for practical usage.
  • a proton-type cation exchange resin can be used semipermanently by regenerating it with hydrochloric acid or the like.
  • the vanadate which is used as a raw material in the ion-exchange polymerization method is not particularly limited, but metavanadate ion is preferable as the vanadate ion (anion), and an alkaline metal ion and/or ammonium ion are preferable as the counter ion (cation).
  • metavanadate ion is preferable as the vanadate ion (anion)
  • an alkaline metal ion and/or ammonium ion are preferable as the counter ion (cation).
  • Concrete examples of the above vanadate are ammonium metavanadate, sodium metavanadate and potassium metavanadate.
  • the proton-type cation exchange resin to be used in the ion-exchange polymerization method is not particularly limited, but a strong acid proton-type cation exchange resin is preferable.
  • the concentration of the vanadate aqueous solution in the ion-exchange polymerization method is not particularly limited, but as to its lower limit, 0.01 mol/L is preferable, 0.03 mol/L is more preferable and 0.05 mol/L is most preferable as vanadate ion. It is not desirable that the concentration of the vanadate aqueous solution be lower than 0.01 mol/L, because the speed of the polymerization is decreased, and the preparation of the catalyst requires too much time.
  • the upper limit represents an amount of melting in water in the saturated state, and for an ammonium metavanadate aqueous solution, the upper limit value is about 0.8 mol/L, and preferably 0.4 mol/L and more preferably 0.2 mol/L.
  • the treating method when a vanadate aqueous solution is subject to ion exchange using a proton-type cation exchange resin is not particularly limited.
  • the vanadate aqueous solution is dripped or flowed in the proton-type cation exchange resin, and the vanadate aqueous solution is contacted with the proton-type cation exchange resin so as to produce cation exchange.
  • a proton-type vanadate aqueous solution can be easily obtained.
  • Various treatment conditions such as treatment time and treatment temperature, are not particularly limited.
  • the above proton-type cation exchange resin can be repeatedly used by regenerating it, for example, with hydrochloric acid or the like.
  • the reaction conditions under which a vanadate aqueous solution is polycondensed are not particularly limited. After being set aside at room temperature for a long time, for example, the vanadate is naturally polycondensed, but its polymerization speed can be increased by heating. It is preferably that the reaction temperature in the case of heating is not higher than 100° C.
  • the reaction time depends upon the reaction temperature and the concentration of the vanadate aqueous solution, but in the case where it is polycondensed at room temperature, for example, not less than one day is preferable and not less than 7 days is more preferable.
  • the vanadate aqueous solution is polycondensed at 80° C., for example, about 3 hours-4 hours is sufficient. As a result, a sol composed of colloidal particles of polyvanadate can be easily obtained.
  • the polymerization degree of the polycondensation is not particularly limited.
  • a drying temperature in the above method is not particularly limited, but its upper limit represents a temperature at which the vanadium pentoxide hydrate to be obtained loses crystallization water and undergoes phase transition to V 2 O 5 (about 350° C.). Therefore, from a viewpoint of stability, a temperature of not higher than 300° C. is preferable and a temperature of not higher than 250° C. is more preferable.
  • the drying may be carried out under normal pressure (atmospheric pressure) or under reduced pressure.
  • the solid acid-base catalyst of the present invention displays sufficient catalytic activity under mild reaction conditions for various reactions, such as syntheses of olefins or ethers through dehydration reactions of alcohols, syntheses of aldehydes or ketones through dehydrogenation reactions of alcohols, hydrations and isomerization reactions of olefins, alkylations, esterifications, amidations, acetalizations, aminations, hydrogen shift reactions, aldol condensation reactions, and polymerization reactions.
  • the reactor which is used for producing various reactions using the solid acid-base catalyst, is not particularly limited, but a fixed-bed flow-type reactor is preferable.
  • the solid acid-base catalyst of the present invention is particularly suitable as a solid acid catalyst which is used for dehydration of alcohols, dehydrogenation of alcohols, isomerization of olefins, esterification of carboxylic acids with alcohols, etc.
  • the solid acid-base catalyst of the present invention when used for the dehydration of an alcohol, a proper ether and/or olefin can be obtained.
  • isopropyl alcohol for example, diisopropyl ether and propylene are obtained.
  • t-butyl alcohol and ethyl alcohol are used, ethyl t-butyl ether and isobutene are obtained.
  • the solid acid-base catalyst is used for dehydrogenation of an alcohol, a proper ketone or aldehyde is obtained.
  • the alcohol is not particularly limited.
  • the reaction conditions such as the amount of the solid acid-base catalyst used with respect to the alcohol, are not particularly limited.
  • the solid acid-base catalyst of the present invention when used for an isomerization reaction of an olefin, a proper isomeric compound is obtained.
  • 1-butene for example, 2-butene is obtained.
  • the olefin is not particularly limited.
  • the reaction conditions, such as the amount of the solid acid-base catalyst used with respect to the olefin are not particularly limited.
  • the solid acid-base catalyst of the present invention when used for an esterification reaction of a carboxylic acid with an alcohol, for example, a proper esterified compound is obtained.
  • a proper esterified compound is obtained.
  • acetic acid and ethyl alcohol for example, ethyl acetate is obtained.
  • the carboxylic acid and the alcohol are not particularly limited.
  • the reaction conditions, such as usage of the solid acid-base catalyst with respect to the carboxylic acid and the alcohol are not particularly limited.
  • the reaction pressure of the above various reactions is not particularly limited.
  • the reaction temperature in these reactions is not particularly limited, but its upper limit value represents a temperature at which the vanadium pentoxide hydrate loses water of crystallization and undergoes phase transition to V 2 O 5 (about 350° C.). Therefore, a temperature of not higher than 300° C. is preferable and not higher than 250° C. is more preferable.
  • the above reaction may be produced under applied pressure or normal pressure (atmospheric pressure) or reduced pressure.
  • the solid acid-base catalyst of the present invention can be suitably used for various reactions, such as syntheses of olefins or ethers through dehydration reactions of alcohols, syntheses of aldehydes and ketones through dehydrogenation reactions of alcohols, hydration and isomerization reactions of olefins, alkylations, esterifications, amidations, acetalizations, aminations, hydrogen shift reactions, aldol condensation reactions and polymerization reactions.
  • various reactions such as syntheses of olefins or ethers through dehydration reactions of alcohols, syntheses of aldehydes and ketones through dehydrogenation reactions of alcohols, hydration and isomerization reactions of olefins, alkylations, esterifications, amidations, acetalizations, aminations, hydrogen shift reactions, aldol condensation reactions and polymerization reactions.
  • the solid acid-base catalyst of the present invention may further contain (intercalate) at least one kind of substance, which is selected from a group composed of metal ions, ammonium ions, metal complexes and organic substances as the occasion demands, besides vanadium pentoxide hydrate.
  • the above-mentioned vanadium pentoxide hydrate has a layer structure, and at least one kind of substance, which is selected from the group composed of metal ions, ammonium ions, metal complexes and organic substances (namely, an intercalant), is intercalated between the layers.
  • metal ions are not particularly limited, but concrete examples are Li + , Na + , K + , Ca 2 , Mg 2+ , Al 3+ , Cu 2+ , Ag + , Ni 2+ , Co 3+ , Fe 3+ and La 3+ .
  • ammonium ions are not limited to NH 4 + , but they may be (alkyl) ammonium ions represented by the following general formula:
  • R 1 , R 2 , R 3 , R 4 each independently represent hydrogen or an alkyl group.
  • metal complexes are not particularly limited, but concretely, metallocene, bipyridyl complex or the like which is a transition metal can be used.
  • organic substances are not particularly limited.
  • a compound containing nitrogen is preferable. Concrete examples of such a compound containing nitrogen are aniline, pyridine, bipyridine, viologen and pyrazine, but the organic substance is not particularly limited to them.
  • the content of the intercalant in the solid acid-base catalyst is not particularly limited, but it is preferable that a molar ratio of the intercalant to V (intercalant/V) is in the range of 0.01-8, and it is more preferable that the molar ration is in the range of 0.1-5.
  • the intercalant may be one kind of substance, which is selected from metal ions, ammonium ions, metal complexes and organic substances, or a plurality of them may be combined.
  • the method of intercalating at least one kind of substance, which is selected from the group composed of metal ions, ammonium ions, metal complexes and organic substances, between the layers of the vanadium pentoxide hydrate as the intercalant is not particularly limited.
  • a powder of a xerogel of a vanadium pentoxide hydrate is soaked into a solution including an intercalant, it may be dried.
  • a hydrogel or a hydrosol of the vanadium pentoxide hydrate is mixed with a solution including an intercalant, it can be dried.
  • salts, metal complexes or organic substances containing metal ions or ammonium ions are directly mixed with a hydrogel or hydrosol of the vanadium pentoxide hydrate, it can be dried.
  • the above-mentioned drying may be carried out in the same manner as that of the case where intercalation is not carried out.
  • the drying temperature is not particularly limited as long as it is not higher than a temperature (about 350° C.) at which vanadium pentoxide hydrate to be obtained loses water of crystallization and undergoes phase transition to V 2 O 5 . Therefore, the temperature can be determined based upon a type of intercalant to be used, but from a viewpoint of stability, a temperature of not higher than 300° C. is preferable and not higher than 250° C. is more preferable.
  • the above drying may be carried out under normal pressure (atmospheric pressure) or reduced pressure.
  • the vanadium pentoxide hydrate is formed at least one kind of substance, which is selected from the group composed of metal ions, ammonium ions, metal complexes and organic substances, is intercalated between the layers of the vanadium pentoxide hydrate with a layered structure, a solid acid-base catalyst having constant catalytic activity can be easily obtained with excellent reproducibility. Furthermore, when an intercalant is selected, the acid-base properties of the solid acid-base catalyst can be adjusted.
  • the solid acid-base catalyst sufficiently displays catalytic activity under mild reaction conditions for various reactions, such as syntheses of olefins or ethers through dehydration reactions of alcohols, syntheses of aldehydes or ketones through dehydrogenation reactions of alcohols, hydrations and isomerization reactions of olefins, alkylations, esterifications, amidations, acetalizations, aminations, hydrogen shift reactions, aldol condensation reactions and polymerization reactions.
  • the reactor which is used for producing the reactions using the solid acid-base catalyst is not particularly limited, although a fixed bed flow-type reactor is preferable.
  • the solid acid-base catalyst in which the intercalant is intercalated between the layers of the vanadium pentoxide hydrate with the layer structure is used for the dehydration and dehydrogenation reactions of alcohols, for example, not only proper ethers and/or olefins but also proper ketones or aldehydes are obtained.
  • alcohols for example, not only proper ethers and/or olefins but also proper ketones or aldehydes are obtained.
  • isopropyl alcohol is used as the alcohol, for example, not only diisopropyl ether and propylene but also acetone are obtained.
  • the alcohol is not particularly limited.
  • the reaction conditions such as the amount of the solid acid-base catalyst used with respect to the alcohol are not particularly limited.
  • the reaction pressure is not particularly limited.
  • the reaction temperature is not particularly limited, but its upper limit value represents a temperature at which the vanadium pentoxide hydrate loses water of crystallization and undergoes phase transition to V 2 O 5 (about 350° C.), so a temperature not higher than 300° C. is preferable and not higher than 250° C. is more preferable.
  • the above reactions may be produced under applied pressure, normal pressure (atmospheric pressure) or reduced pressure.
  • the catalytic activity of the solid acid-base catalyst of the present invention can be further improved.
  • the solid acid-base catalyst of the present invention can be suitably used for various reactions, such as syntheses of olefins or ethers through hydration reactions of alcohols, syntheses of aldehydes or ketones through dehydrogenation reactions of alcohols, hydrations and isomerization reactions of olefins, alkylations, esterifications, amidations, acetalizations, aminations, hydrogen shift reactions, aldol condensation reactions and polymerization reactions.
  • various reactions such as syntheses of olefins or ethers through hydration reactions of alcohols, syntheses of aldehydes or ketones through dehydrogenation reactions of alcohols, hydrations and isomerization reactions of olefins, alkylations, esterifications, amidations, acetalizations, aminations, hydrogen shift reactions, aldol condensation reactions and polymerization reactions.
  • the polyvanadic acid sol was dried in air at 120° C. for one whole day and night, and then calcined in air at 250° C. for two hours so that a blackish brown xerogel was obtained.
  • the xerogel was ground for 10 minutes by a ball mill and the obtained powder was press molded, its grain size was made uniform to 9 mesh-16 mesh so that a solid acid-base catalyst was obtained.
  • the solid acid-base catalyst obtained in the above method an X-ray diffraction spectrum was measured, and its substance was identified. As a result, it was confirmed that the solid acid-base catalyst contains vanadium pentoxide hydrate represented by the general equation (1). Moreover, it was confirmed that the vanadium pentoxide hydrate had a layer crystal structure in which an interlayer spacing was 11.5 ⁇ in air at room temperature and that “n” of the general equation (1) was 1.6.
  • the X-ray diffraction spectrum is shown in FIG. 1 .
  • an ether was synthesized through a dehydration reaction of an alcohol. Namely, in order to conduct the reaction using a fixed bed flow method, 1.0 g of the solid acid-base catalyst was charged into a reactor constructed of stainless steel with an internal diameter of 10 mm. Then, a mixed gas, which was obtained by mixing t butyl alcohol, ethyl alcohol and helium so that the molar ratio became 1:1:15 was passed through the reactor at a speed of 64 ml/min. The reaction conditions were normal pressure and a temperature of 90° C.
  • the mixed gas which had passed through the reactor for 15 minutes immediately after the start of the reaction, was sampled, and its product was analyzed by gas chromatography.
  • conversion of the t-butyl alcohol was 28.2% and conversion of the ethyl alcohol was 16.0%.
  • the selectivity of ethyl t-butyl ether, which is a product was 44.3% on a basis of the t-butyl alcohol and 78.1% on a basis of the ethyl alcohol.
  • the selectivity of isobutene which is a product was 35.7%.
  • the mixed gas which had passed through the reactor for 15 minutes immediately after the start of the reaction, was sampled, and its product was analyzed by gas chromatography.
  • conversion of the isopropyl alcohol was 73.7%.
  • an isomerization reaction of an olefin was conducted. Namely, 1.2 g of the solid acid-base catalyst was charged into a reactor which is similar to the above one. Then, a mixed gas, which was obtained by mixing 1-butene and helium so that the molar ratio became 1:10.5, was passed through the reactor at a speed of 46 ml/min. The reaction conditions were normal pressure and a temperature of 160° C.
  • the mixed gas which had passed through the reactor for 15 minutes immediately after the start of the reaction, was sampled, and its product was analyzed by gas chromatography.
  • conversion of the 1-butene was 12.6%.
  • an esterification reaction was conducted. Namely, 1.2 g of the solid acid-base catalyst was charged into a reactor which is similar to the above one. Then, a mixed gas, which was obtained by mixing acetic acid, ethyl alcohol and helium so that the molar ratio became 1:1.7:12.7, was passed through the reactor at a speed of 65 ml/min. The reaction conditions were normal pressure and a temperature of 140° C.
  • the mixed gas which had passed through the reactor for 15 minutes immediately after the start of the reaction, was sampled, and its product was analyzed by gas chromatography.
  • conversion of the acetic acid was 16.6%
  • conversion of the ethyl alcohol was 17.5%
  • the selectivity of ethyl acetate, which is a product was 85.5% on a basis of the acetic acid and 47.7% on a basis of the ethyl alcohol.
  • the polyvanadic acid sol obtained in example 1 was dried at 200° C. so that a blackish brown xerogel was obtained. Then, after the xerogel was ground for 10 minutes by a ball mill, the resultant powder was press molded so that a grain size was made uniform to 9 mesh -16 mesh and a solid acid-base catalyst was obtained.
  • the solid acid-base catalyst obtained in the above method when an X-ray diffraction spectrum was measured, the spectrum was completely the same as the X-ray diffraction spectrum of the solid acid-base catalyst in example 1 and shown in FIG. 1 . Namely, it was confirmed that the solid acid-base catalyst contains vanadium pentoxide hydrate represented by the general equation (1). Moreover, it was confirmed that the vanadium pentoxide hydrate had a layer crystal structure in which an interlayer spacing was 11.5 ⁇ in air at room temperature and that “n” of the general equation (1) was 1.6.
  • the mixed gas which had passed through the reactor for 15 minutes immediately after the starting of the reaction, was sampled, and its product was analyzed by gas chromatography.
  • conversion of the isopropyl alcohol was 37.5%.
  • the solid acid-base catalyst obtained in the above method when its X-ray diffraction spectrum was measured, it was confirmed that its diffraction pattern was completely the same as the diffraction pattern of the vanadium pentoxide hydrate which was obtained in example 1 and shown in FIG. 1 and that its layer crystal structure was maintained. Moreover, it was confirmed that a peak position of the X-ray diffraction spectrum of the solid acid-base catalyst was shifted from the peak position of the X-ray diffraction spectrum of the vanadium pentoxide hydrate, which was obtained in example 1 and shown in FIG. 1, and that the interlayer spacing of the layer crystal structure was changed to 13.0 ⁇ .
  • the mixed gas which had passed through the reactor for 15 minutes immediately after the start of the reaction, was sampled, and its products were analyzed by gas chromatography.
  • conversion of the isopropyl alcohol was 55.4%.
  • selectivity of acetone and propylene, which are products was respectively 44.4% and 39.6%. Further, at this time, diisopropyl ether was not formed.
  • the polyvanadic acid sol of example 1 was diluted with water, and 2.5 liters of a liquid whose concentration as vanadium ion was 0.03 mol/L was obtained.
  • the solid acid-base catalyst obtained in the above manner when its X-ray diffraction spectrum was measured, it was confirmed that its diffraction pattern was completely the same as the diffraction pattern of the vanadium pentoxide hydrate which was obtained in example 1 and shown in FIG. 1 and that its layer crystal structure was maintained. Moreover, it was confirmed that a peak position of the X-ray diffraction spectrum of the solid acid-base catalyst was shifted from the peak position of the X-ray diffraction spectrum of the vanadium pentoxide hydrate, which was obtained in example 1 and shown in FIG. 1, and that the interlayer spacing of the layer crystal structure was changed to 11.3 ⁇ .
  • the mixed gas which had passed through the reactor for 15 minutes immediately after the start of the reaction, was sampled, and products were analyzed by gas chromatography.
  • conversion of the isopropyl alcohol was 50.7%.
  • the polyvanadic acid sol of example 1 was diluted with water, and 2.5 liters of a liquid whose concentration as vanadium ion was 0.03 mol/L was obtained. 300 mL of water, in which 31.87 g of NaNO 3 was dissolved, was added to the liquid, and it was agitated at room temperature for 1 hour. After a formed brown precipitate was filtered, and agitation and rinsing of the precipitate for 30 minutes using 2 liters of water were repeated twice, the precipitate was dried at 200° C. Then, after the precipitate was ground for 10 minutes by a ball mill and the resultant powder was press molded, its grain size was made uniform to 9 mesh-16 mesh so that a solid acid-base catalyst was obtained.
  • the solid acid-base catalyst obtained in the above method when its X-ray diffraction spectrum was measured, it was confirmed that its diffraction pattern was completely the same as the diffraction pattern of the vanadium pentoxide hydrate which was obtained in example 1 and shown in FIG. 1 and that its layer crystal structure was maintained. Moreover, it was confirmed that a peak position of the X-ray diffraction spectrum of the solid acid-base catalyst was shifted from the peak position of the X-ray diffraction spectrum of the vanadium pentoxide hydrate, which was obtained in example 1 and shown in FIG. 1, and that the interlayer spacing of the layer crystal structure was changed to 11.1 ⁇ .
  • the Na + was intercalated between the layers of the vanadium pentoxide hydrate having the layer crystal structure.
  • the molar ratio of the intercalated Na + was 1.24 with respect to V.
  • the mixed gas which had passed through the reactor for 15 minutes immediately after the start of the reaction, was sampled, and products were analyzed by gas chromatography.
  • conversion of the isopropyl alcohol was 21.1%.
  • the polyvanadic acid sol of example 1 was diluted with water, and 2.5 liters of a liquid whose concentration as vanadium ion was 0.03 mol/L was obtained. 300 mL of water, in which 37.90 g of KNO 3 was dissolved, was added to the liquid, and it was agitated at room temperature for 1 hour. After a formed brown precipitate was filtered, and agitation and rinsing of the precipitate for 30 minutes using 2 liters of water were repeated twice, the precipitate was dried at 200° C. Then, after the precipitate was ground for 10 minutes by a ball mill and the resultant powder was press molded, its grain size was made uniform to 9 mesh-16 mesh so that a solid acid-base catalyst was obtained.
  • the solid acid-base catalyst obtained in the above manner when its X-ray diffraction spectrum was measured, it was confirmed that its diffraction pattern was completely the same as the diffraction pattern of the vanadium pentoxide hydrate which was obtained in example 1 and shown in FIG. 1 and that its layer crystal structure was maintained. Moreover, it was confirmed that a peak position of the X-ray diffraction spectrum of the solid acid-base catalyst was shifted from the peak position of the X-ray diffraction spectrum of the vanadium pentoxide hydrate, which was obtained in example 1 and shown in FIG. 1, and that the interlayer spacing of the layer crystal structure was changed to 10.9 ⁇ .
  • the K + was intercalated between the layers of the vanadium pentoxide hydrate having the layer crystal structure.
  • the molar ratio of the intercalated K + was 0.41 with respect to V.
  • the mixed gas which had passed through the reactor for 15 minutes immediately after the start of the reaction, was sampled, and products were analyzed by gas chromatography.
  • conversion of the isopropyl alcohol was 30.7%.
  • the polyvanadic acid sol of example 1 was diluted with water, and 2.5 liters of a liquid whose concentration as vanadium ion was 0.03 mol/L was obtained.
  • the solid acid-base catalyst obtained in the above manner when its X-ray diffraction spectrum was measured, it was confirmed that its diffraction pattern was completely the same as the diffraction pattern of the vanadium pentoxide hydrate which was obtained in example 1 and shown in FIG. 1 and that its layer crystal structure was maintained. Moreover, it was confirmed that a peak position of the X-ray diffraction spectrum of the solid acid-base catalyst was shifted from the peak position of the X-ray diffraction spectrum of the vanadium pentoxide hydrate, which was obtained in example 1 and shown in FIG. 1, and that the interlayer spacing of the layer crystal structure was changed to 13.4 ⁇ .
  • the Mg 2+ was intercalated between the layers of the vanadium pentoxide hydrate having the layer crystal structure.
  • the molar ratio of the intercalated Mg 2+ was 3.88 with respect to V.
  • the mixed gas which had passed through the reactor for 15 minutes immediately after the start of the reaction, was sampled, and products were analyzed by gas chromatography.
  • conversion of the isopropyl alcohol was 39.2%.
  • the polyvanadic acid sol of example 1 was diluted with water, and 2.5 liters of a liquid whose concentration as vanadium ion was 0.03 mol/L was obtained.
  • the solid acid-base catalyst obtained in the above manner when its X-ray diffraction spectrum was measured, it was confirmed that its diffraction pattern was completely the same as the diffraction pattern of the vanadium pentoxide hydrate which was obtained in example 1 and shown in FIG. 1 and that its layer crystal structure was maintained. Moreover, it was confirmed that a peak position of the X-ray diffraction spectrum of the solid acid-base catalyst was shifted from the peak position of the X-ray diffraction spectrum of the vanadium pentoxide hydrate, which was obtained in example 1 and shown in FIG. 1, and that the interlayer spacing of the layer crystal structure was changed to 12.9 ⁇ .
  • the mixed gas which had passed through the reactor for 15 minutes immediately after the start of the reaction, was sampled, and products were analyzed by gas chromatography.
  • conversion of the isopropyl alcohol was 30.9%.
  • the polyvanadic acid sol of example 1 was diluted with water, and 2.5 liters of a liquid whose concentration as vanadium ion was 0.03 mol/L was obtained. 300 mL of water, in which 28.13 g of Al(NO 3 ) 3 ⁇ 9H 2 O was dissolved, was added to the liquid, and it was agitated at room temperature for 1 hour. After a created brown precipitate was filtered, and agitation and rinsing of the precipitate for 30 minutes using 2 liters of water were repeated twice, the precipitate was dried at 200° C. Then, after the precipitate was ground for 10 minutes by a ball mill and the resultant powder was press molded, its grain size was made uniform to 9 mesh-16 mesh so that a solid acid-base catalyst was obtained.
  • the solid acid-base catalyst obtained in the above manner when its X-ray diffraction spectrum was measured, it was confirmed that its diffraction pattern was completely the same as the diffraction pattern of the vanadium pentoxide hydrate which was obtained in example 1 and shown in FIG. 1 and that its layer crystal structure was maintained. Moreover, it was confirmed that a peak position of the X-ray diffraction spectrum of the solid acid-base catalyst was shifted from the peak position of the X-ray diffraction spectrum of the vanadium pentoxide hydrate, which was obtained in example 1 and shown in FIG. 1, and that the interlayer spacing of the layer crystal structure was changed to 13.6 ⁇ .
  • the Al 3+ was intercalated between the layers of the vanadium pentoxide hydrate having the layer crystal structure.
  • the molar ratio of the intercalated Al 3+ was 3.52 with respect to V.
  • the mixed gas which had passed through the reactor f or 15 minutes immediately after the start of the reaction, was sampled, and products were analyzed by gas chromatography.
  • conversion of the isopropyl alcohol was 35.3%.

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Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2134543A (en) 1937-06-09 1938-10-25 Rohm & Haas Vanadium oxide catalyst
US2409587A (en) 1944-08-25 1946-10-15 Albert A F Maxwell Combination hydrocarbon dehydrogenation and hydrogenation process
US2510803A (en) 1948-05-13 1950-06-06 Pittsburgh Coke & Chemical Co Vanadium pentoxide catalysts
US3689515A (en) 1971-06-04 1972-09-05 Foote Mineral Co Vanadyl oxalate compounds and process for producing same
JPS49116008A (de) 1973-03-15 1974-11-06
DE2408910A1 (de) 1974-02-25 1975-09-18 Elektrometallurgie Gmbh Verwendung einer vanadinpentoxid-gallerte
US4011278A (en) * 1963-02-27 1977-03-08 Mobil Oil Corporation Conversion of polar compounds using a zsm-5 zeolite catalyst
DE3006287A1 (de) 1980-02-20 1981-10-08 Stahlwerke Peine-Salzgitter Ag, 3150 Peine Verfahren zur gewinnung von vanadinpentoxid-hydrat und duengemittel aus fluessigem, phosphorhaltigem roheisen mit einem siliziumgehalt von kleiner/gleich 0,1%
JPS61293940A (ja) 1985-06-18 1986-12-24 Sumitomo Chem Co Ltd アルコ−ル類の製造法
JPH01224365A (ja) 1988-03-03 1989-09-07 Koei Chem Co Ltd ２−ピラジンカルボキサミド　４−オキシドの製造方法
EP0350344A1 (de) 1988-06-10 1990-01-10 Rhone-Poulenc Chimie Lamellare intercolierte metallische Oxyde und Verfahren zu ihrer Herstellung
JPH0578130A (ja) 1991-09-20 1993-03-30 Nippon Sheet Glass Co Ltd 繊維構造を有するバナジウム酸化物の製造方法
JPH0623043A (ja) 1990-11-27 1994-02-01 Wr Grace & Co Connecticut 全血からの低密度リポ蛋白−コレステロールの高性能除去
EP0582822A1 (de) 1992-06-30 1994-02-16 Millipore Corporation Prüfung von Membranen
US5496787A (en) 1993-01-29 1996-03-05 Mitsubishi Chemical Corporation Process for producing a vanadium-phosphorus oxide catalyst precursor
EP0747123A2 (de) * 1995-06-08 1996-12-11 Nippon Shokubai Co., Ltd. Fester Säure-Base-Katalysator

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2134543A (en) 1937-06-09 1938-10-25 Rohm & Haas Vanadium oxide catalyst
US2409587A (en) 1944-08-25 1946-10-15 Albert A F Maxwell Combination hydrocarbon dehydrogenation and hydrogenation process
US2510803A (en) 1948-05-13 1950-06-06 Pittsburgh Coke & Chemical Co Vanadium pentoxide catalysts
US4011278A (en) * 1963-02-27 1977-03-08 Mobil Oil Corporation Conversion of polar compounds using a zsm-5 zeolite catalyst
US3689515A (en) 1971-06-04 1972-09-05 Foote Mineral Co Vanadyl oxalate compounds and process for producing same
JPS49116008A (de) 1973-03-15 1974-11-06
DE2408910A1 (de) 1974-02-25 1975-09-18 Elektrometallurgie Gmbh Verwendung einer vanadinpentoxid-gallerte
DE3006287A1 (de) 1980-02-20 1981-10-08 Stahlwerke Peine-Salzgitter Ag, 3150 Peine Verfahren zur gewinnung von vanadinpentoxid-hydrat und duengemittel aus fluessigem, phosphorhaltigem roheisen mit einem siliziumgehalt von kleiner/gleich 0,1%
JPS61293940A (ja) 1985-06-18 1986-12-24 Sumitomo Chem Co Ltd アルコ−ル類の製造法
JPH01224365A (ja) 1988-03-03 1989-09-07 Koei Chem Co Ltd ２−ピラジンカルボキサミド　４−オキシドの製造方法
EP0350344A1 (de) 1988-06-10 1990-01-10 Rhone-Poulenc Chimie Lamellare intercolierte metallische Oxyde und Verfahren zu ihrer Herstellung
JPH0244010A (ja) 1988-06-10 1990-02-14 Rhone Poulenc Chim 架橋した薄層構造を持つ金属酸化物の製造方法及び得られる金属酸化物
US5073360A (en) * 1988-06-10 1991-12-17 Rhone-Poulenc Chimie Bridge/lamellar metallic oxides
JPH0623043A (ja) 1990-11-27 1994-02-01 Wr Grace & Co Connecticut 全血からの低密度リポ蛋白−コレステロールの高性能除去
JPH0578130A (ja) 1991-09-20 1993-03-30 Nippon Sheet Glass Co Ltd 繊維構造を有するバナジウム酸化物の製造方法
EP0582822A1 (de) 1992-06-30 1994-02-16 Millipore Corporation Prüfung von Membranen
US5496787A (en) 1993-01-29 1996-03-05 Mitsubishi Chemical Corporation Process for producing a vanadium-phosphorus oxide catalyst precursor
EP0747123A2 (de) * 1995-06-08 1996-12-11 Nippon Shokubai Co., Ltd. Fester Säure-Base-Katalysator

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
Aldebert et al., "V2O5 gels; a versatile host structure for intercalation" Revue de Chimie Minerale, vol. 19, 1982, pp. 485-495.
Handy et al., "Vanadia, Vanadia-Titania, and Vanadia-Titania-Silica Gels . . . ", 134 Journal of Catalysis 75-86 (1992).
Hiroshi Hirashima et al., Jnl of Japan Ceramics Assn., 97 [3] 234-38, 1989, "Synthesis of V2O2 Gels from Vanadyl Alkoxides.".
Kanatzidis et al., "Conductive Polymer Bronzes. Intercalated Polyaniline in V2O5Xerogels," 111 J. Am. Chem. Soc. 4139-4141 (1989).
Kittaka et al., "Thermal Desorption of n-Alchols Intercalated in Vanadium Pentaoxide Hydrate," 89(20) J. Chem. Soc. Faraday Trans. 3827-3832 (1993).
N.V. Sidgwick, "The Chemical Elements and Their Compounds", vol. 1. pp. 810-811 (1950).
Pozarnsky et al., "51V NMR and EPR Study of Reaction Kinetics and Mechanisms in V2O5 . . . " 6 Chem. Mater. 380-385 (1994).
Ruiz-Hitzky, E. et al.; "Interlayer Adsorption of Ammonia and Pyridine in V2O5 Xerogel"; Journal of the Chemical Society, Faraday Trans. 1; vol. 82, pp. 1597-1604 (1986).

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EP0747123A2 (de) 1996-12-11
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EP0747123B1 (de) 2003-09-24
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